Fungicide mixture

ABSTRACT

Fungicidal mixtures, comprising as active components 
     a) a compound of the formula I                    
      its N-oxide or one of its salts where: 
     R 1 , R 2 , R 3 , R 4  independently of one another are: hydrogen, hydroxyl, nitro, halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 -haloalkylthio; 
     R 5 , R 6 , R 7  independently of one another are: hydrogen, hydroxyl, cyano, nitro, halogen, C 1 -C 7 -alkyl, C 1 -C 7 -haloalkyl, C 1 -C 7 -alkoxy, C 1 -C 7 -haloalkoxy, C 1 -C 7 -alkylthio, C 1 -C 7 -haloalkylthio, C 1 -C 7 -hydroxyalkyl, C 2 -C 4 -acyl, aryl, aryloxy, where the radicals with aryl may for their part carry one to three of the following groups: cyano, nitro, halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkylthio and C 1 -C 4 -haloalkylthio, and 
     b) carbamates of the formula II,                    
     in which T is CH or N, n is 0, 1 or 2 and R is halogen, C 1 -C 4 -alkyl or C 1 -C 4 -haloalkyl, where the radicals R may be different if n is 2, 
     in a synergistically effective amount.

This application is a 371 of PCT/EP99/09812, filed on Dec. 11, 1999which claims priority of DE 19859250.7 filed on Dec. 22, 1998.

The present invention relates to a fungicidal mixture comprising

a) a compound of the formula I

 its N-oxide or one of its salts where:

R¹, R², R³, R⁴ independently of one another are: hydrogen, hydroxyl,nitro, halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio;

R⁵, R⁶, R⁷ independently of one another are: hydrogen, hydroxyl, cyano,nitro, halogen, C₁-C₇-alkyl, C₁-C₇-haloalkyl, C₁-C₇-alkoxy,C₁-C₇-haloalkoxy, C₁-C₇-alkylthio, C₁-C₇-haloalkylthio,C₁-C₇-hydroxyalkyl, C₂-C₄-acyl, aryl, aryloxy, where the radicals witharyl may for their part carry one to three of the following groups:cyano, nitro, halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,C₁-C₄-haloalkoxy, C₁-C₄-alkylthio and C₁-C₄-haloalkylthio, and

b) a compound of the formula II,

in which T is CH or N, n is 0, 1 or 2 and R is halogen, C₁-C₄-alkyl orC₁-C₄-haloalkyl, where the radicals R may be different if n is 2,

in a synergistically effective amount.

Moreover, the invention relates to methods for controlling harmful fungiusing the compounds I and the compounds II or synergistic mixturescomprising them, and to the use of the compounds I or the compounds IIfor preparing such mixtures.

Compounds of the formula I, their fungicidal action and theirpreparation are known from U.S. Pat. No. 5,240,940 and from ACS Sympos.Ser. 443, page 538 to page 552 (1991).

The compounds of the formula II, their preparation and their actionagainst harmful fungi are likewise known from the literature (WO-A96/01,256 and 96/01,258).

It is an object of the present invention to provide mixtures which, at areduced total amount of active compounds applied, have an improvedaction against harmful fungi (synergistic mixtures), with a view toreducing the application rates and improving the activity spectrum ofthe known compounds.

We have found that this object is achieved by the mixtures defined atthe outset. Furthermore, we have found that, if the compounds I and thecompounds II are applied simultaneously, i.e. jointly or separately, orif the compounds I and the compounds II are applied successively,harmful fungi can be controlled better than with the compounds I or IIon their own.

Owing to the basic character of the nitrogen ring atom or the NHgrouping, the compounds I and II are capable of forming salts withinorganic or organic acids or with metal ions.

Examples of inorganic acids are hydrohalic acids, such as hydrogenfluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide,sulfuric acid, phosphoric acid and nitric acid or carbonic acid.

Suitable organic acids are, for example: formic acid and alkanoic acids,such as acetic acid, trifluoroacetic acid, trichloroacetic acid andpropionic acid, and also glycolic acid, thiocyanic acid, lactic acid,succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid,alkylsulfonic acids (sulfonic acids having straight-chain or branchedalkyl radicals of from 1 to 20 carbon atoms), arylsulfonic acids oraryldisulfonic acids (aromatic radicals, such as phenyl and naphthyl,which carry one or two sulfo groups), alkylphosphonic acids (phosphonicacids having straight-chain or branched alkyl radicals of from 1 to 20carbon atoms), arylphosphonic acids or aryldiphosphonic acids (aromaticradicals, such as phenyl and naphthyl, which carry one or two phosphonicacid radicals), it being possible for the alkyl or aryl radicals tocarry further substituents, for example p-toluene sulfonic acid,salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid,2-acetoxybenzoic acid, etc.

Suitable metal ions are, in particular, the ions of the elements of thesecond main group, in particular calcium and magnesium, the third andfourth main group, in particular aluminum, tin and lead, and the firstto eighth sub-group, in particular chromium, manganese, iron, cobalt,nickel, copper, zinc. Particular preference is given to the metal ionsof the elements of the sub-groups of the fourth period. The metals canexist in the various valencies which they can assume.

Furthermore, the compounds I can be converted in a manner known per seinto the N-oxides (cf. U.S. Pat. No. 5,240,940).

With respect to the C═Y or C═CH or C═N double bonds, the compounds ofthe formula II can be present in the E or the Z configuration (withrespect to the carboxylic acid function). Accordingly, they can be usedin the mixture according to the invention in each case either as pure Eor Z isomers or as E/Z isomer mixtures. Preference is given to using theE/Z isomer mixture or the Z isomer, and particular preference is givento the Z isomer.

The C═N double bonds of the oxime ether groupings in the side chain ofthe compounds II can in each case be present as pure E or Z isomers oras E/Z isomer mixtures. The compounds II can be used in the mixturesaccording to the invention both as isomer mixtures and as pure isomers.With respect to their use, particular preference is given to compoundsII in which the terminal oxime ether grouping of the side chain ispresent in the cis configuration (OCH₃ to COOCH₃).

For providing the fungicidal mixtures according to the invention,preference is given to using compounds I, their salts or N-oxides inwhich:

R¹, R², R³, R⁴ independently of one another are hydrogen, halogen,C₁-C₂-alkyl, C₁-C₂-haloalkyl, C₁-C₂-alkoxy, C₁-C₂-haloalkoxy orC₁-C₂-alkylthio;

R⁵, R⁶, R⁷ independently of one another are hydrogen, nitro, cyano,halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy or phenyl.

With respect to the suitability for use as mixing partners, particularpreference is given to the compounds Ia of Table 1 below.

TABLE 1 (Ia)

No. R¹ R² R³ R⁴ R⁵ I.1  H H Cl H 2-F I.2  H H Cl H 2-C(CH₃)₃ I.3  H H ClH 2-CH₃ I.4  H H Cl H 2-OCH₃ I.5  H H Cl H 3-F I.6  H H Cl H 3-Cl I.7  HH Cl H 3-CF₃ I.8  H H Cl H 3-CN I.9  H H Cl H 3-OCH₃ I.10 H H Cl H3-phenyl I.11 H H Cl H 4-Cl I.12 H H Cl H 4-Br I.13 H H Cl H 4-CF₃ I.14H H Cl H 4-CH₃ I.15 H H Cl H 4-CH(CH₃)₂ I.16 H H Cl H 4-CN I.17 H H Cl H2-Cl-4-F I.18 H H Cl H 2,4-di-Br I.19 H H Cl H 2,4-di-NO₂ I.20 H H Cl H2-CH₃-4-F I.21 H H Cl H 2,6-di-F I.22 H H Cl H 2,4,6-tri-CH₃ I.23 F H HH 4-F I.24 Cl H H H 4-F I.25 NO₂ H H H 4-F I.26 H F H H 4-F I.27 H Cl HH 4-F I.28 H CH₃ H H 4-F I.29 H NO₂ H H 4-F I.30 H OC₂H₅ H H 4-F I.31 HH F H 4-F I.32 H H Cl H 4-F I.33 H H Br H 4-F I.34 H H NO₂ H 4-F I.35 HH OCF₃ H 4-F I.36 H H C₂H₅ H 4-F I.37 H H SCF₃ H 4-F I.38 H H O—C₂H₅ H4-F I.39 H H H F 4-F I.40 H H H Cl 4-F I.41 H H H CF3 4-F I.42 F H F H4-F I.43 O—CH₃ H O—CH₃ H 4-F I.44 Cl F H H 4-F I.45 Cl Cl H H 4-F I.46Cl CH₃ H H 4-F I.47 H Br H Cl 4-F I.48 H Cl H OH 4-F I.49 H O—CH₃ H NO₂4-F I.50 H F Cl H 4-F I.51 H CH₃ Cl H 4-F I.52 H H Cl Cl 4-F I.53 Cl H HCl 4-F I.54 Cl F Cl H 4-F I.55 H H Cl CN 4-F I.56 Cl CH₃ Cl H 4-F I.57Cl Cl Cl H 4-F I.58 Cl Cl Cl Cl 4-F I.59 H H H Cl 2-F-4-Br I.60 H H H Cl2,3-di-CH₃ I.61 H H H Cl 2-F-4-Cl I.62 H H H Cl 2,4-di-Cl-6-F I.63 H H HCl 2,4-di-F I.64 H H H Cl 2,4-di-CH₃ I.65 H H H Cl 2-C₂H₅ I.66 H H H Cl2-CH₃-4-F I.67 H H H Cl 3-CH₃-4-Cl I.68 H H Cl H H I.69 Cl H Cl H H I.70H H Cl H 4-C(CH₃)₃

Very particular preference is given to the compounds Ia of Table 2 andto the hydrochloride and the N-oxide of the compound 8 mentionedtherein.

TABLE 2 No. R¹ R² R³ R⁴ R⁵ 1.71 H H Cl H 2-Cl 1.72 H H Cl H 2-Br 1.73 HH Cl H 2-CN 1.74 H H Cl H 2-CF₃ 1.75 H H Cl H 2-NO₂ 1.76 H H Cl H 4-F1.77 H H Cl H 2,4-di-F 1.78 Cl H Cl H 4-F 1.79 H H H Cl 2-Cl-4-F 1.80CH₃ H CH₃ H 4-F

The compounds of the formula Ia mentioned in or under Tables 1 and 2 areknown from U.S. Pat. No. 5,240,940 and/or ACS Sympos. Ser. 443, page 538to page 552 (1991). Compound I.78 of Table 2 is known under the commonname quinoxyfen.

For providing the fungicidal mixtures according to the invention,preference is given to compounds II in which T and R are as defined inTable 3.

TABLE 3 No. T R_(n) II.1 N 2-F II.2 N 3-F II.3 N 4-F II.4 N 2-Cl II.5 N3-Cl II.6 N 4-Cl II.7 N 2-Br II.8 N 3-Br II.9 N 4-Br II.10 N 2-CH₃ II.11N 3-CH₃ II.12 N 4-CH₃ II.13 N 2-CH₂CH₃ II.14 N 3-CH₂CH₃ II.15 N 4-CH₂CH₃II.16 N 2-CH(CH₃)₂ II.17 N 3-CH(CH₃)₂ II.18 N 4-CH(CH₃)₂ II.19 N 2-CF₃II.20 N 3-CF₃ II.21 N 4-CF₃ II.22 N 2,4-F₂ II.23 N 2,4-Cl₂ II.24 N3,4-Cl₂ II.25 N 2-Cl 4-CH₃ II.26 N 3-Cl 4-CH₃ II.27 CH 2-F II.28 CH 3-FII.29 CH 4-F II.30 CH 2-Cl II.31 CH 3-Cl II.32 CH 4-Cl II.33 CH 2-BrII.34 CH 3-Br II.35 CH 4-Br II.36 CH 2-CH₃ II.37 CH 3-CH₃ II.38 CH 4-CH₃II.39 CH 2-CH₂CH₃ II.40 CH 3-CH₂CH₃ II.41 CH 4-CH₂CH₃ II.42 CH2-CH(CH₃)₂ II.43 CH 3-CH(CH₃)₂ II.44 CH 4-CH(CH₃)₂ II.45 CH 2-CF₃ II.46CH 3-CF₃ II.47 CH 4-CF₃ II.48 CH 2,4-F₂ II.49 CH 2,4-Cl₂ II.50 CH3,4-Cl₂ II.51 CH 2-Cl 4-CH₃ II.52 CH 3-Cl 4-CH₃

Particular preference is given to the compounds II.12, II.23, II.32 andII.38.

In some cases, it has been found to be advantageous to use otherfungicidally active compounds in addition to the fungicidally activecompounds I and II in the mixtures according to the invention. Mentionmay be made in particular of active compounds from the group of theazoles or the morpholine and piperidine derivatives.

Particularly preferred azoles are the compounds mentioned below:

bromuconazole, Proc. Br. Crop Prot. Conf.-Pests Dis., 5-6, 439 (1990);

cyproconazole, U.S. Pat. No. 4,664,696;

difenoconazole, GB-A 2,098,607;

diniconazole, CAS RN [83657-24-3];

epoxiconazole, EP-A 196 038;

fenbuconazole (proposed), EP-A 251 775;

fluquinconazole, Proc. Br. Crop Prot. Conf.-Pests Dis., 5-3, 411 (1992);

flusilazole, Proc. Br. Crop Prot. Conf.-Pests Dis., 1, 413 (1984);

hexaconazole, CAS RN [79983-71-4];

metconazole, Proc. Br. Crop Prot. Conf.-Pests Dis., 5-4, 419 (1992);

prochloraz, U.S. Pat. No. 3,991,071;

propiconazole, GB-A 1,522,657;

tebuconazole, U.S. Pat. No. 4,723,984;

tetraconazole, Proc. Br. Crop Prot. Conf.-Pests Dis., 1, 49 (1988);

triflumizole, JP-A 79/119,462

flutriafol, CAS RN [76674-21-0]

myclobutanil, CAS RN [88671-89-0].

A particularly preferred mixing partner is epoxiconazole.

In such ternary mixtures, the ratios of the triazoles to the compounds Iand II are generally in the range of from 20:1 to 1:20, preferably from10:1 to 1:10.

Suitable morpholine or piperidine derivatives are, in particular, theknown active compounds tridemorph, fenpropidin and fenpropimorph, whichare commercially available. Particular preference is given here tofenpropimorph. The ratios of the morpholine or piperidine derivatives tothe compounds I and II are generally in the range of from 50:1 to 1:10,preferably from 25:1 to 1:1.

Finally, in some other cases it has been found to be advantageous to usequaternary mixtures which, in addition to compounds I and II, comprise atriazole and a morpholine or piperidine derivative. A mixture which ispreferred in practice is a mixture of compounds I (in particularcompound I.78 from Table 2), compounds II (preferably compounds II.32 orII.38 from Table 3), epoxiconazole and fenpropimorph.

When preparing the mixtures, it is preferred to employ the pure activecompounds I and II, to which further active compounds against harmfulfungi or other pests, such as insects, arachnids or nematodes, or elseherbicidal or growth-regulating active compounds or fertilizers can beadmixed, as required.

The mixtures of the compounds I and II, or the compounds I and II,applied simultaneously, i.e. jointly or separately, or successively,exhibit outstanding activity against a wide range of phytopathogenicfungi, in particular from the classes of the Ascomycetes,Deuteromycetes, Phycomycetes and Basidiomycetes. Some of them actsystemically and can therefore be employed as foliar- and soil-actingfungicides.

They are especially important for controlling a large number of fungi ina variety of crop plants, such as cotton, vegetable species (for examplecucumbers, beans and cucurbits), barley, grass, oats, coffee, maize,fruit species, rice, rye, soya, grapevine, wheat, ornamentals,sugarcane, and a variety of seeds.

They are particularly suitable for controlling the followingphytopathogenic fungi: Erysiphe graminis (powdery mildew) in cereals,Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,Podosphaera leucotricha in apples, Puccinia species in cereals,Rhizoctonia species in cotton and lawns, Ustilago species in cereals andsugarcane, Venturia inaequalis (scab) in apples, Helminthosporiumspecies in cereals, Septoria nodorum in wheat, Botrytis cinerea (graymold) in strawberries and grapes, Cercospora arachidicola in groundnuts,Pseudocercosporella herpotrichoides in wheat and barley, Pyriculariaoryzae in rice, Phytophthora infestans in potatoes and tomatoes,Plasmopara viticola in grapes, Alternaria species in vegetables andfruit, and also Fusarium and Verticillium species.

Furthermore, they can be used in the protection of materials (forexample in the protection of wood), for example against Paecilomycesvariotii.

The compounds I and II can be applied simultaneously, i.e. together orseparately, or in succession, the sequence, in the case of separateapplication, generally not having any effect on the result of thecontrol measures.

The compounds I and II are usually used in a weight ratio of from 50:1to 0.1:1, preferably from 25:1 to 0.5:1, in particular from 10:1 to 1:1.

Depending on the kind of effect desired, the application rates of themixtures according to the invention are from 0.01 to 3 kg/ha, preferablyfrom 0.1 to 1.5 kg/ha, in particular from 0.4 to 1.0 kg/ha.

The application rates of the compounds I are from 0.01 to 0.5 kg/ha,preferably from 0.05 to 0.5 kg/ha, in particular from 0.05 to 0.2 kg/ha.

Depending on the kind of effect desired, the application rates of themixtures according to the invention for the compounds II are from 0.005to 0.5 kg/ha, preferably from 0.05 to 0.5 kg/ha, in particular from 0.05to 0.2 kg/ha.

For seed treatment, the application rates of the mixture are generallyfrom 0.001 to 50 g/kg of seed, preferably from 0.01 to 10 g/kg, inparticular from 0.01 to 8 g/kg.

If phytopathogenic fungi are to be controlled, the separate or jointapplication of the compounds I and II or of the mixtures of thecompounds I and II is effected by spraying or dusting the seeds, theplants or the soils before or after sowing of the plants, or before orafter plant emergence.

The fungicidal synergistic mixtures according to the invention, or thecompounds I and II, can be formulated, for example, in the form ofdirectly sprayable solutions, powders and suspensions or in the form ofhighly concentrated aqueous, oily or other suspensions, dispersions,emulsions, oil dispersions, pastes, dusts, materials for broadcasting orgranules, and applied by spraying, atomizing, dusting, broadcasting orwatering. The use form depends on the intended purpose; in any case, itshould ensure as fine and uniform as possible a distribution of themixture according to the invention.

The formulations are prepared in a manner known per se, for example byadding solvents and/or carriers. It is usual to admix inert additives,such as emulsifiers or dispersants, with the formulations.

Suitable surfactants are the alkali metal salts, alkaline earth metalsalts and ammonium salts of aromatic sulfonic acids, for example ligno-,phenol-, naphthalene- and dibutylnaphthalene-sulfonic acid, and of fattyacids, alkyl- and alkylaryl-sulfonates, alkyl, lauryl ether and fattyalcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols,or of fatty alcohol glycol ethers, condensates of sulfonated naphthaleneand its derivatives with formaldehyde, condensates of naphthalene or ofthe naphthalenesulfonic acids with phenol and formaldehyde,polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- ornonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycolethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcoholethylene oxide condensates, ethoxylated castor oil, polyoxyethylenealkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycolether acetate, sorbitol esters, lignosulfite waste liquors or methylcellulose.

Powders, materials for broadcasting and dusts can be prepared by mixingor jointly grinding the compounds I and II, or the mixtures of thecompounds I and II with a solid carrier.

Granules (for example coated granules, impregnated granules orhomogeneous granules) are usually prepared by binding the activecompound, or active compounds, to a solid carrier.

Fillers or solid carriers are, for example, mineral earths, such assilicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk,bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate,magnesium sulfate, magnesium oxide, ground synthetic materials andfertilizers, such as ammonium sulfate, ammonium phosphate, ammoniumnitrate, ureas, and products of vegetable origin, such as cereal meal,tree bark meal, wood meal and nutshell meal, cellulose powders or othersolid carriers.

The formulations generally comprise from 0.1 to 95% by weight,preferably from 0.5 to 90% by weight, of one of the compounds I and II.The active compounds are employed in a purity of from 90% to 100%,preferably from 95% to 100% (according to NMR spectrum or HPLC).

The compounds I and II, or the mixtures, or the correspondingformulations, are applied by treating the harmful fungi or the plants,seeds, soils, areas, materials or spaces to be kept free from them witha fungicidally effective amount of the mixture, or of the compounds Iand II in the case of separate application. Application can be effectedbefore or after infection by the harmful fungi.

The fungicidal activity of the compounds and the mixtures can bedemonstrated by the following experiments:

The active compounds, separately or together, are formulated as a 10%strength emulsion in a mixture of 70% by weight of cyclohexanone, 20% byweight of Nekanil® LN (Lutensol® AP6, wetting agent having emulsifyingand dispersing action based on ethoxylated alkylphenols) and 10% byweight of Emulphor® EL (Emulan® EL, emulsifier based on ethoxylatedfatty alcohols) and diluted with water to the desired concentration.

Evaluation is carried out by determining the infected leaf areas inpercent. These percentages are converted into efficacies. The expectedefficacies of the mixtures of the active compounds are determined usingColby's formula [R. S. Colby, Weeds 15, 20-22 (1967)] and compared withthe observed efficacies.

Colby's formula:

E=x+y+z−x·y·z/100

E expected efficacy, expressed in % of the untreated control, when usingthe mixture of the active compounds A, B and C at the concentrations a,b and c

x efficacy, expressed in % of the untreated control, when using activecompound A at a concentration of a

y efficacy, expressed in % of the untreated control, when using activecompound B at a concentration of b

z efficacy, expressed in % of the untreated control, when using activecompound C at a concentration of c

The efficacy (E) is calculated as follows using Abbot's formula:

E=(1−α/β)·100

α corresponds to the fungal infection of the treated plants in % and

β corresponds to the fungal infection of the untreated (control) plantsin %

At an efficacy of 0, the infection level of the treated plantscorresponds to that of the untreated control plants; at an efficacy of100, the treated plants are not infected.

USE EXAMPLE 1

Action Against Mildew of Wheat

Leaves of wheat seedlings of the cultivar “Kanzler”, grown in pots, weresprayed to run-off point with an aqueous formulation of activeingredient which had been prepared using a stock solution comprising 10%of active ingredient, 63% of cyclohexanone and 27% of emulsifier, and 24h after the spraycoating had dried on the leaves were dusted with sporesof mildew of wheat (Erysiphe graminis forma specialis tritici). The testplants were subsequently placed in climatized chambers at 20-24° C. and60-90% relative atmospheric humidity for 7 days. The extent of thedevelopment of the disease on the leaves was then evaluated visually.

The visually determined values for the percentage of diseased leaf areawere converted into efficacies in % of the untreated control. Anefficacy of 0 means the same disease level as in the untreated control,an efficacy of 100 means a disease level of 0%. The expected efficaciesfor the active ingredient combinations were determined using Colby'sformula (Colby, S. R. “Calculating synergistic and antagonisticresponses of herbicide combinations”, Weeds, 15, pp. 20-22, 1967) andcompared with the observed efficacies.

The components II were the compounds II.23, II.32 and II.38 from Table3.

Active Efficacy in % of the Ex. ingredient conc. in ppm untreatedcontrol 1C without (90% diseased) 0 2C Compound I.78 1 33 (common name:0.25 0 quinoxyfen) 0.06 0 3C Compound II.23 4 78 1 67 0.25 11 0.06 0 4CCompound II.32 1 67 0.25 11 0.06 0 5C Compound II.38 4 78 1 67 0.25 110.06 0

TABLE 5 Mixture according to the invention Observed Calculated Ex.(conc. in ppm) efficacy efficacy* 6   1 ppm I.78 + 93 78   1 ppm II.23 70.25 ppm I.78 + 44 11 0.25 ppm II.23 8 0.06 ppm I.78 + 21 0 0.06 ppmII.23 9   1 ppm I.78 + 97 85   4 ppm II.23 10 0.25 ppm I.78 + 94 67   1ppm II.23 11   1 ppm I.78 + 56 41 0.25 ppm II.23 12 0.25 ppm I.78 + 21 00.06 ppm II.23 13   1 ppm I.78 + 94 78   1 ppm II.32 14 0.25 ppm I.78 +56 11 0.25 ppm II.32 15 0.06 ppm I.78 + 21 0 0.06 ppm II.32 16 0.06 ppmI.78 + 32 11 0.25 ppm II.32 17   1 ppm I.78 + 78 41 0.25 ppm II.32 180.25 ppm I.78 + 21 0 0.06 ppm II.32 19   1 ppm I.78 + 93 78   1 ppmII.38 20 0.25 ppm I.78 + 32 11 0.25 ppm II.38 21 0.06 ppm I.78 + 21 00.06 ppm II.38 22   1 ppm I.78 + 100 85   4 ppm II.38 23   1 ppm I.78 +67 41 0.25 ppm II.38 24 0.25 ppm I.78 + 21 0 0.06 ppm II.38 *Calculatedusing Colby's formula

The test results show that for all mixing ratios the observed efficacyis higher than the efficacy which had been calculated beforehand usingColby's formula.

We claim:
 1. A fungicidal composition comprising, as active components,a) a compound of formula I

 its N-oxide or one of its salts where: R¹, R², R³, R⁴ independently ofone another are: hydrogen, hydroxyl, nitro, halogen, C₁-C₄-alkyl,C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio,C₁-C₄-haloalkylthio; R⁵, R⁶, R⁷ independently of one another are:hydrogen, hydroxyl, cyano, nitro, halogen, C₁-C₇-alkyl, C₁-C₇-haloalkyl,C₁-C₇-alkoxy, C₁-C₇-haloalkoxy, C₁-C₇-alkylthio, C₁-C₇-haloalkylthio,C₁-C₇-hydroxyalkyl, C₂-C₄-acyl, aryl, aryloxy, where the radicals witharyl may for their part carry one to three of the following groups:cyano, nitro, halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,C₁-C₄-haloalkoxy, C₁-C₄-alkylthio and C₁-C₄-haloalkylthio, and b) atleast one carbamate of formula II,

wherein T is CH or N, n is 0, 1 or 2 and R is halogen, C₁-C₄-alkyl orC₁-C₄-haloalkyl, and where the radicals R are identical or differentwhen n is 2, wherein the active components (a) and (b) are present insynergistically effective amounts.
 2. The composition defined in claim1, wherein the components (a) and (b) are present in a weight ratio offrom 20:1 to 1:20.
 3. The composition defined in claim 1, whichcomprises as a further active component an effective amount of afungicidal triazole.
 4. The composition defined in claim 1, whichcomprises as a further active component an effective amount of one ormore compounds selected from the group consisting of fenpropimorph,fenpropidin and tridodemorph.
 5. The composition defined in claim 3,which comprises as a further active component an effective amount, ofone or more compounds selected from the group consisting offenpropimorph, fenpropidin and tridemorph.
 6. A method for controllingharmful fungi, which comprises treating the harmful fungi, their habitator plants, seeds, soils, areas, materials or spaces to be kept from saidfungi with an effective amount of the composition defined in claim
 1. 7.The method of claim 6, wherein the active components (a) and (b) areapplied simultaneously either jointly or separately, or successively. 8.The method of in claim 6, wherein the the active component (a) isapplied in an amount of from 0.01 to 0.5 kg/ha.
 9. A process forpreparing the composition defined in claim 1, which comprises admixingsynergistically effective amounts of the active components (a) and (b).10. The composition defined in claim 1 which is conditioned in twoparts, one part comprising the component (a) in a solid or liquidcarrier and the other part comprising the component (b) in a a solid orliquid carrier.
 11. The composition defined in claim 3, wherein thefungicidal triazole is selected from the group consisting ofbromuconazole, cyproconazole, difenoconazole, diniconazole,epoxiconazole, fenbuconazole, fluquinconazole, flusilazole,hexaconazole, metconazole, prochloraz, propiconazole, tebuconazole,tetraconazole, triflumizole, flutriafol and myclobutanil.
 12. Thecomposition defined in claim 3, wherein the further active component andthe components (a) and (b) are present in a weight ratio of from 20:1 to1:20.
 13. The composition defined in claim 4, wherein the further activecomponent and the components (a) and (b) are present in a weight ratioof from 50:1 to 1:10.